US11155771B2 - Method for preparing a liquid washing or cleaning agent using a preservative-free dye solution - Google Patents
Method for preparing a liquid washing or cleaning agent using a preservative-free dye solution Download PDFInfo
- Publication number
- US11155771B2 US11155771B2 US16/186,172 US201816186172A US11155771B2 US 11155771 B2 US11155771 B2 US 11155771B2 US 201816186172 A US201816186172 A US 201816186172A US 11155771 B2 US11155771 B2 US 11155771B2
- Authority
- US
- United States
- Prior art keywords
- dye
- acid
- dye solution
- washing
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000005406 washing Methods 0.000 title claims abstract description 43
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000007788 liquid Substances 0.000 title claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 21
- 239000003755 preservative agent Substances 0.000 claims abstract description 9
- 238000011437 continuous method Methods 0.000 claims abstract description 6
- 239000000975 dye Substances 0.000 claims description 80
- 239000000203 mixture Substances 0.000 claims description 31
- -1 builders Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 102000004190 Enzymes Human genes 0.000 claims description 13
- 108090000790 Enzymes Proteins 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 3
- 229920003169 water-soluble polymer Polymers 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 230000002335 preservative effect Effects 0.000 claims 1
- 239000006254 rheological additive Substances 0.000 claims 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 29
- 239000000049 pigment Substances 0.000 description 26
- 239000003795 chemical substances by application Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 19
- 239000003945 anionic surfactant Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 150000002191 fatty alcohols Chemical class 0.000 description 13
- 239000000344 soap Substances 0.000 description 13
- 239000010457 zeolite Substances 0.000 description 13
- 229940088598 enzyme Drugs 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 12
- 239000002736 nonionic surfactant Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- 150000007513 acids Chemical class 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 8
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- FZUOVNMHEAPVBW-UHFFFAOYSA-L quinoline yellow ws Chemical compound [Na+].[Na+].O=C1C2=CC=CC=C2C(=O)C1C1=NC2=C(S([O-])(=O)=O)C=C(S(=O)(=O)[O-])C=C2C=C1 FZUOVNMHEAPVBW-UHFFFAOYSA-L 0.000 description 8
- UJMBCXLDXJUMFB-GLCFPVLVSA-K tartrazine Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-GLCFPVLVSA-K 0.000 description 8
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- 239000007844 bleaching agent Substances 0.000 description 7
- 235000019425 dextrin Nutrition 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
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- 235000012756 tartrazine Nutrition 0.000 description 7
- 239000004149 tartrazine Substances 0.000 description 7
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 7
- 229920002245 Dextrose equivalent Polymers 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
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- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- 235000013162 Cocos nucifera Nutrition 0.000 description 5
- 244000060011 Cocos nucifera Species 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 235000012752 quinoline yellow Nutrition 0.000 description 5
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical class COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- RTMBGDBBDQKNNZ-UHFFFAOYSA-L C.I. Acid Blue 3 Chemical compound [Ca+2].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=C(O)C=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1.C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=C(O)C=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 RTMBGDBBDQKNNZ-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 4
- 108091005804 Peptidases Proteins 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000004365 Protease Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- OIQPTROHQCGFEF-UHFFFAOYSA-L chembl1371409 Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 OIQPTROHQCGFEF-UHFFFAOYSA-L 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- SXQCTESRRZBPHJ-UHFFFAOYSA-M lissamine rhodamine Chemical compound [Na+].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=C(S([O-])(=O)=O)C=C1S([O-])(=O)=O SXQCTESRRZBPHJ-UHFFFAOYSA-M 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 235000012736 patent blue V Nutrition 0.000 description 4
- 239000002304 perfume Substances 0.000 description 4
- 229910052615 phyllosilicate Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- AXMCIYLNKNGNOT-UHFFFAOYSA-N sodium;3-[[4-[(4-dimethylazaniumylidenecyclohexa-2,5-dien-1-ylidene)-[4-[ethyl-[(3-sulfophenyl)methyl]amino]phenyl]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 AXMCIYLNKNGNOT-UHFFFAOYSA-N 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 102000013142 Amylases Human genes 0.000 description 3
- 108010065511 Amylases Proteins 0.000 description 3
- HMEKVHWROSNWPD-UHFFFAOYSA-N Erioglaucine A Chemical compound [NH4+].[NH4+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 HMEKVHWROSNWPD-UHFFFAOYSA-N 0.000 description 3
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
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- 150000008051 alkyl sulfates Chemical class 0.000 description 3
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
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- 229920001577 copolymer Polymers 0.000 description 3
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- 239000008103 glucose Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000005858 glycosidation reaction Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229940059442 hemicellulase Drugs 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229910052739 hydrogen Chemical group 0.000 description 1
- 239000001257 hydrogen Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- 229940040461 lipase Drugs 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229940100573 methylpropanediol Drugs 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- CTIQLGJVGNGFEW-UHFFFAOYSA-L naphthol yellow S Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C([O-])=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 CTIQLGJVGNGFEW-UHFFFAOYSA-L 0.000 description 1
- 229910021527 natrosilite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SXLLDUPXUVRMEE-UHFFFAOYSA-N nonanediperoxoic acid Chemical compound OOC(=O)CCCCCCCC(=O)OO SXLLDUPXUVRMEE-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 235000019419 proteases Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- LGZQSRCLLIPAEE-UHFFFAOYSA-M sodium 1-[(4-sulfonaphthalen-1-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C(S([O-])(=O)=O)C2=C1 LGZQSRCLLIPAEE-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 108010038851 tannase Proteins 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical group OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
Definitions
- the present invention relates to a continuous method for preparing a liquid washing or cleaning agent which comprises at least one surfactant and at least one dye.
- the dye solution used in the method according to the invention is free of preservatives.
- the present invention also relates to washing or cleaning agents which are obtained by means of the method according to the invention.
- washing and cleaning agents are increasingly being prepared in continuous methods.
- a dye solution is usually also dosed into the preparation method.
- this dye solution In order to prevent this dye solution from being contaminated, it has to be microbiologically stabilized.
- the present invention therefore relates to a continuous method for preparing a liquid washing or cleaning agent comprising at least one surfactant and at least one dye, the method comprising the following steps:
- the present invention relates to washing or cleaning agents which are obtained by means of the method according to the invention.
- the present invention also relates to preservative-free dye solutions, the dye first being dissolved in water and this premixture subsequently being diluted in a non-aqueous organic solvent, the content of the organic solvent being at least 70 wt. % based on the total weight of the dye solution.
- At least one also refers to one or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.
- this expression refers to the type of agent/compound and not to the absolute number of molecules.
- the problems arising from the prior art are solved by the dye solution being prepared using a non-aqueous substance system.
- the dye is first dissolved in a small amount of water in order to dissolve said dye completely.
- the concentration of the dye in the aqueous premixture preferably corresponds to at least 400 times, more preferably at least 600 times, particularly preferably 800 times to 5,000 times, and in particular 900 times to 2,000 times, the target concentration of dye desired in the final product.
- the premixture obtained in this way is then diluted using an organic, water-miscible solvent. This dilution is necessary to obtain a solution that can be continuously dosed with sufficient accuracy.
- the dye solution obtained in this way which comprises substantially organic solvents as solvents, is then dosed into a surfactant-containing liquid flow.
- a surfactant-containing liquid flow it may be necessary for the dye solution to be mixed with the surfactant-containing liquid flow by means of a mixer.
- the mixer can be a dynamic or static mixer.
- a content of organic solvent of at least 70 wt. % in the dye solution ensures that microbiological preservation is not necessary.
- the content of an organic solvent is preferably at least 80 wt. % and more preferably at least 90 wt. %.
- the dye is a conventional dye which can be used for various washing or cleaning agents.
- the dye is preferably selected from Acid Red 18 (CI 16255), Acid Red 26, Acid Red 27, Acid Red 33, Acid Red 51, Acid Red 87, Acid Red 88, Acid Red 92, Acid Red 95, Acid Red 249 (CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet 48, Acid Violet 54, Acid Yellow 1, Acid Yellow 3 (CI 47005), Acid Yellow 11, Acid Yellow 23 (CI 19140), Acid Yellow 3, Direct Blue 199 (CI 74190), Direct Yellow 28 (CI 19555), Food Blue 2 (CI 42090), Food Blue 5:2 (CI 42051:2), Food Red 7 (CI 16255), Food Yellow 13 (CI 47005), Food Yellow 3 (CI 15985), Food Yellow 4 (CI 19140), Reactive Green 12 and Solvent Green 7 (CI 59040).
- Particularly preferred dyes are water-soluble acid dyes, for example Food Yellow 13 (Acid Yellow 3, CI 47005), Food Yellow 4 (Acid Yellow 23, CI 19140), Food Red 7 (Acid Red 18, CI 16255), Food Blue 2 (Acid Blue 9, CI 42090), Food Blue 5 (Acid Blue 3, CI 42051), Acid Red 249 (CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet 48, Acid Blue 80 (CI 61585), Acid Blue 182, Acid Blue 182, Acid Green 25 (CI 61570) and Acid Green 81.
- Food Yellow 13 Acid Yellow 3, CI 47005
- Food Yellow 4 Acid Yellow 23, CI 19140
- Food Red 7 Acid Red 18, CI 16255
- Food Blue 2 Acid Blue 9, CI 42090
- Food Blue 5 Acid Blue 3, CI 42051
- Acid Red 249 CI 18134
- Acid Red 52 CI 45100
- Acid Violet 126 Acid Violet 48
- Acid Blue 80 CI 61585
- Acid Blue 182 Acid
- Water-soluble direct dyes for example Direct Yellow 28 (CI 19555) and Direct Blue 199 (CI 74190)
- water-soluble reactive dyes for example Reactive Green 12
- the dyes Food Yellow 3 (CI 15985) and Acid Yellow 184 are equally preferably used.
- Aqueous dispersions of the following pigment dyes are equally preferably used: Pigment Black 7 (CI 77266), Pigment Blue 15 (CI 74160), Pigment Blue 15:1 (CI 74160), Pigment Blue 15:3 (CI 74160), Pigment Green 7 (CI 74260), Pigment Orange 5, Pigment Red 112 (CI 12370), Pigment Red 112 (CI 12370), Pigment Red 122 (CI 73915), Pigment Red 179 (CI 71130), Pigment Red 184 (CI 12487), Pigment Red 188 (CI 12467), Pigment Red 4 (CI 12085), Pigment Red 5 (CI 12490), Pigment Red 9, Pigment Violet 23 (CI 51319), Pigment Yellow 1 (CI 28 11680), Pigment Yellow 13 (CI 21100), Pigment Yellow 154, Pigment Yellow 3 (CI 11710), Pigment Yellow 74, Pigment Yellow 83 (CI 21108) and Pigment Yellow 97.
- the following pigment dyes are used in the form of dispersions: Pigment Yellow 1 (CI 11680), Pigment Yellow 3 (CI 11710), Pigment Red 112 (CI 12370), Pigment Red 5 (CI 12490), Pigment Red 181 (CI 73360), Pigment Violet 23 (CI 51319), Pigment Blue 15:1 (CI 74160), Pigment Green 7 (CI 74260) and Pigment Black 7 (CI 77266).
- water-soluble polymer dyes are used, for example Liquitint, Liquitint Blue HP, Liquitint Blue MC, Liquitint Blue 65, Liquitint Cyan 15, Liquitint Patent Blue, Liquitint Violet 129, Liquitint Royal Blue, Liquitint Experimental Yellow 8949-43, Liquitint Green HMC, Liquitint Yellow LP, Liquitint Yellow II and mixtures thereof.
- water-soluble dyes is particularly preferred, the use of water-soluble polymer dyes being more particularly preferred.
- the group of more particularly preferred dyes includes Acid Blue 3, Acid Yellow 23, Acid Red 33, Acid Violet 126, Liquitint Yellow LP, Liquitint Cyan 15, Liquitint Blue HP and Liquitint Blue MC.
- the method according to the invention also comprises the dye solution being dosed in a surfactant-containing liquid flow.
- the liquid washing or cleaning agent obtained thus comprises at least one surfactant.
- the at least one surfactant can in this case be selected from anionic surfactants, non-ionic surfactants, cationic surfactants and zwitterionic surfactants.
- the washing or cleaning agent preferably comprises at least one anionic surfactant and/or at least one non-ionic surfactant.
- Washing or cleaning agents which comprise at least one alkylbenzene sulfonate as an anionic surfactant are particularly suitable.
- the at least one alkylbenzene sulfonate is particularly preferably a linear or branched C 6-19 alkylbenzene sulfonate, preferably a linear C 9-13 alkylbenzene sulfonate.
- Anionic surfactants that are used are those of the sulfonate and sulfate types, for example.
- Surfactants of the sulfonate type that can be used are preferably C 9-13 alkylbenzene sulfonates, olefin sulfonates, which is to say mixtures of alkene and hydroxyalkane sulfonates, and disulfonates, as obtained, for example, from C 12-18 monoolefins having a terminal or internal double bond by way of sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products.
- Alkane sulfonates obtained from C 12-18 alkanes for example by way of sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable.
- the esters of ⁇ -sulfofatty acids are suitable, for example the ⁇ -sulfonated methyl esters of hydrogenated coconut fatty acids, palm kernel fatty acids or tallow fatty acids.
- Suitable alkylbenzene sulfonates are preferably selected from linear or branched alkylbenzene sulfonates of formula
- R′ and R′′ independently of one another, are H or alkyl, and together contain 6 to 19, preferably 7 to 15, and in particular 9 to 13, C atoms.
- a more particularly preferred representative is sodium dodecylbenzene sulfonate.
- alkali salts and in particular the sodium salts of the sulfuric acid half-esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, or of C 10 -C 20 oxo alcohols and the half-esters of secondary alcohols having this chain length are preferred as alk(en)yl sulfates.
- Alk(en)yl sulfates having the described chain length that include a synthetic straight-chain alkyl functional group prepared on a petrochemical basis, and have a degradation behavior similar to that of the adequate compounds based on fatty chemical raw materials, are also preferred. From a washing perspective, the C 12 -C 16 alkyl sulfates, C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
- the sulfuric acid monoesters of straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols having, on average, 3.5 mol ethylene oxide (EO) or C 12-18 fatty alcohols having 1 to 4 EO, are also suitable.
- Suitable alkyl ether sulfates are, for example, compounds of formula A-1 R 1 —O-(AO) n —SO 3 ⁇ X + (A-1)
- R 1 represents a linear or branched, substituted or unsubstituted alkyl functional group, preferably a linear, unsubstituted alkyl functional group, particularly preferably a fatty alcohol functional group.
- Preferred functional groups R are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl functional groups and mixtures thereof, the representatives which have an even number of C atoms being preferred.
- Particularly preferred functional groups R 1 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol or from C 10 -C 20 oxo alcohols.
- AO represents an ethylene oxide (EO) group or propylene oxide (PO) group, preferably an ethylene oxide group.
- the index n represents an integer from 1 to 50, preferably from 1 to 20, and in particular from 2 to 10. More particularly preferably, n represents the numbers 2, 3, 4, 5, 6, 7 or 8.
- X represents a monovalent cation or the n-th part of an n-valent cation, in this case the alkali metal ions, which include Na + or K + , being preferred, Na + being most preferred.
- Further cations X + can be selected from NH 4 + , 1 ⁇ 2 Mg 2+ , 1 ⁇ 2 Ca 2+ , 1 ⁇ 2 Mn 2+ , and mixtures thereof.
- alkylether sulfate can be selected from fatty alcohol ether sulfates of formula A-2.
- the degree of ethoxylation indicated represents a statistical average that can correspond to an integer or a fractional number for a specific product.
- the degrees of alkoxylation indicated represent statistical averages that can correspond to an integer or a fractional number for a specific product.
- Preferred alkoxylates/ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE).
- anionic surfactant is understood not to mean soaps. Although the washing or cleaning agents according to the invention may comprise soaps, these are not classified as anionic surfactants within the meaning of the present invention.
- soaps are considered additional components of the washing or cleaning agents.
- Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, such as coconut fatty acids, palm kernel fatty acids or tallow fatty acids.
- the anionic surfactants, as well as soaps can be present in the form of the sodium, potassium or ammonium salts thereof, and as soluble salts of organic bases, such as monoethanolamine, diethanolamine or triethanolamine.
- the anionic surfactants and soaps are preferably present in the form of the sodium, potassium or magnesium salts thereof, in particular in the form of the sodium salts.
- Anionic surfactants that are preferably used are in this case the alkylbenzene sulfonates and fatty alcohol sulfates, in particular the alkylbenzene sulfonates.
- the proportion of soap is preferably from 0.1 to 1 wt. %, in particular from 0.1 to 0.7 wt. % or from 0.2 to 0.5 wt. %, based on the total weight of the washing or cleaning agent.
- the washing or cleaning agents may also contain further conventional ingredients of agents of this kind.
- further surfactants in particular non-ionic surfactants, builder substances, bleaching agents, enzymes and other active substances should be mentioned.
- the washing or cleaning agent may contain further ingredients which further improve the practical and/or aesthetic properties of the washing agent.
- the washing or cleaning agent preferably additionally contains one or more substances from the group comprising enzymes, bleaching agents, bleach activators, complexing agents, builders, electrolytes, non-aqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescing agents, optical brighteners, dyes, speckles, hydrotropic substances, silicone oils, anti-redeposition agents, graying inhibitors, anti-shrink agents, anti-crease agents, dye transfer inhibitors, antimicrobial active ingredients, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, anti-swelling and anti-slip agents, softening components and UV absorbers.
- the washing or cleaning agents according to the invention as defined herein do not comprise soaps, the compositions may nevertheless comprise speckles which comprise soap fractions. In this case, the composition only comprises soaps in the speckles.
- Non-ionic surfactants that are preferably used are alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 C atoms and, on average, 1 to 12 mol of ethylene oxide (EO) per mol of alcohol, in which the alcohol functional group can be linear or preferably methyl-branched in the 2 position, or can contain linear and methyl-branched functional groups in admixture, as are usually present in oxo alcohol functional groups.
- EO ethylene oxide
- alcohol ethoxylates having linear functional groups of alcohols of native origin having 12 to 18 C atoms, for example of coconut, palm, tallow fatty or oleyl alcohol, and an average of 2 to 8 EO per mol of alcohol are particularly preferred.
- Examples of preferred ethoxylated alcohols are C 12-14 alcohols having 3 EO or 4 EO, C 9-11 n-alcohols having 7 EO, C 13-15 alcohols having 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols having 3 EO, 5 EO or 7 EO, and mixtures thereof, such as mixtures of C 12-14 alcohol having 3 EO and C 12-18 alcohol having 5 EO.
- the degrees of ethoxylation indicated represent statistical averages that can correspond to an integer or a fractional number for a specific product.
- Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols having more than 12 EO can also be used. Examples of these are tallow fatty alcohols having 14 EO, 25 EO, 30 EO, or 40 EO.
- non-ionic surfactants that are preferably used, which are used either as the sole non-ionic surfactant or in combination with other non-ionic surfactants, is alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.
- alkyl polyglycosides Another class of non-ionic surfactants that can advantageously be used is the alkyl polyglycosides (APG).
- Alkyl polyglycosides that can be used have the general formula RO(G) z , in which R represents a linear or branched, in particular methyl-branched at the 2-position, saturated or unsaturated aliphatic functional group having 8 to 22, preferably 12 to 18, C atoms, and G is the symbol that represents a glycose unit having 5 or 6 C atoms, preferably glucose.
- the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0, and in particular between 1.1 and 1.4.
- Linear alkyl polyglycosides are preferably used, which is to say alkyl polyglycosides in which the polyglycol functional group is a glucose functional group and the alkyl functional group is an n-alkyl functional group.
- Non-ionic surfactants of the amine oxide type for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallow alkyl-N,N-dihydroxyethylamine oxide, and of the fatty acid alkanolamides can also be suitable.
- the amount of these non-ionic surfactants is preferably no more than that of the ethoxylated fatty alcohols, in particular no more than half thereof.
- Builder substances are another significant group of washing or cleaning agent ingredients. This substance class is understood to cover both organic and inorganic builder substances. These are compounds which may carry out a supporting function in the agents according to the invention and also act as a water softening substance when in use.
- Usable organic builder substances are, for example, the polycarboxylic acids that can be used in the form of the sodium salts thereof, polycarboxylic acids being understood to mean those carboxylic acids that carry more than one acid function. These include, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that the use thereof is not objectionable for ecological reasons, and mixtures thereof.
- NTA nitrilotriacetic acid
- Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, saccharic acids, and mixtures thereof.
- the acids can also be used per se.
- the acids typically also have the property of being an acidification component and are thus also used, for example in the granules according to the invention, for setting a lower and milder pH of washing or cleaning agents.
- Particularly noteworthy here are citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof.
- Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g/mol. This substance class has already been described in detail above.
- the (co)polymeric polycarboxylates may be used either as a powder or an aqueous solution.
- the content of (co)polymeric polycarboxylates in the agent is preferably from 0.5 to 20 wt. %, in particular from 3 to 10 wt. %.
- the polymers can also contain allyl sulfonic acids, such as allyloxybenzene sulfonic acid and methallyl sulfonic acid in EP-B-0 727 448, as a monomer.
- allyl sulfonic acids such as allyloxybenzene sulfonic acid and methallyl sulfonic acid in EP-B-0 727 448.
- Biodegradable polymers composed of more than two different monomer units are also particularly preferred, for example those that, according to DE-A-43 00 772, contain salts of acrylic acid and of maleic acid, and vinyl alcohol or vinyl alcohol derivatives as monomers or, according to DE-C-42 21 381, salts of acrylic acid and of 2-alkylallylsulfonic acid and sugar derivatives as monomers.
- copolymers are those that are described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably comprise acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate as monomers.
- Polymeric aminodicarboxylic acids, the salts thereof or the precursors thereof should likewise be mentioned as further preferred builders.
- Polyaspartic acids or the salts and derivatives thereof are particularly preferred, of which it is disclosed in the German patent application DE-A-195 40 086 that they also exhibit a bleach-stabilizing effect, in addition to co-builder properties.
- polyacetals which may be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in the European patent application EP-A-0 280 223.
- Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof, and from polyol carboxylic acids such as gluconic acid and/or glucoheptonic acid.
- dextrins for example oligomers or polymers of carbohydrates, which can be obtained by the partial hydrolysis of starches.
- the hydrolysis can be carried out according to customary, for example acid- or enzyme-catalyzed, methods.
- These dextrins are preferably hydrolysis products having an average molar mass in the range of from 400 to 500,000 g/mol.
- a polysaccharide having a dextrose equivalent (DE) in the range of from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100.
- DE dextrose equivalent
- Oxidized dextrins of this kind and methods for the preparation thereof are known, for example, from the European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496, and the international patent applications WO 92/18542, WO-A-93/08251, WO-A-93/16110, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608.
- An oxidized oligosaccharide according to the German patent application DE-A-196 00 018 is also suitable.
- a product that is oxidized on C 6 of the saccharide ring can be particularly advantageous.
- Ethylenediamine-N,N′-disuccinate (EDDS) the synthesis of which is described in U.S. Pat. No. 3,158,615, for example, is preferably used in the form of the sodium or magnesium salts thereof.
- Suitable amounts for use in zeolite-containing and/or silicate-containing formulations are from 3 to 15 wt. %.
- organic cobuilders that can be used are, for example, acetylated hydroxycarboxylic acids or the salts thereof, which optionally can also be present in lactone form and comprise at least 4 carbon atoms and at least one hydroxy group, as well as no more than two acid groups. Cobuilders of this kind are described, for example, in the international patent application WO-A-95/20029.
- a further class of substances having cobuilder properties is phosphonates. These include, in particular, hydroxyalkane and aminoalkane phosphonates. Of the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as a sodium salt, the disodium salt reacting neutral and the tetrasodium salt reacting alkaline (pH 9). Possible preferable aminoalkane phosphonates include ethylenediamine tetramethylene phosphonate (EDTMP), diethylentriamine pentamethylene phosphonate (DTPMP) and the higher homologs thereof.
- ETMP ethylenediamine tetramethylene phosphonate
- DTPMP diethylentriamine pentamethylene phosphonate
- HEDP hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP.
- HEDP hexasodium salt of EDTMP
- HEDP hepta- and octa-sodium salt of DTPMP.
- the aminoalkane phosphonates additionally have a pronounced heavy-metal-binding power. Accordingly, it may be preferred, in particular if the agents also include bleach, to use aminoalkane phosphonates, in particular DTPMP, or to use mixtures of the mentioned phosphonates.
- all compounds that are able to form complexes with alkaline earth ions can be used as cobuilders.
- a preferably used inorganic builder is finely crystalline, synthetic and bound-water-containing zeolite.
- the finely crystalline, synthetic and bound-water-containing zeolite used is preferably zeolite A and/or P.
- Zeolite X and mixtures of A, X and/or P, for example a co-crystallizate from zeolites A and X are also suitable, however.
- the zeolite can be used as a spray-dried powder or also as an undried, stabilized suspension that is still moist from its preparation process. If zeolite is used in the form of a suspension, it may contain small additional amounts of non-ionic surfactants as stabilizers, for example from 1 to 3 wt.
- zeolites based on the zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups, C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measuring method: Coulter counter) and preferably contain from 18 to 22 wt. %, and in particular from 20 to 22 wt. %, of bound water.
- zeolites are contained in the premix in amounts of from 10 to 94.5 wt. %, it being particularly preferable for zeolite to be contained in amounts of from 20 to 70 wt. %, in particular from 30 to 60 wt. %.
- Suitable partial substitutes for zeolites are phyllosilicates of natural and synthetic origin.
- Phyllosilicates of this kind are known from patent applications DE-A-23 34 899, EP-A-0 026 529 and DE-A-35 26 405, for example.
- the usability thereof is not limited to a specific composition or structural formula.
- smectites are preferred, in particular bentonites.
- Crystalline, layered sodium silicates of the general formula NaMSi x O 2x+1 yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, and preferred values for x are 2, 3 or 4, are also suitable as zeolite or phosphate substitutes.
- Crystalline phyllosilicates of this kind are described, for example, in European patent application EP-A-0 164 514.
- Preferred crystalline phyllosilicates of the aforementioned formula are those in which M represents sodium and x assumes the values 2 or 3. Both ß- and ⁇ -sodium disilicates Na 2 Si 2 O 5 yH 2 O are particularly preferred.
- the preferred builders can also include amorphous sodium silicates which have a Na 2 O:SiO 2 modulus of from 1:2 to 1:3.3, preferably from 1:2 to 1:2.8, and in particular from 1:2 to 1:2.6, and preferably have retarded dissolution and secondary washing properties.
- the retarded dissolution compared to conventional amorphous sodium silicates can have been caused in a variety of ways, for example by way of surface treatment, compounding, compacting/compression or over-drying.
- amorphous is also understood to mean “X-ray amorphous.” This means that the silicates do not supply any sharp X-ray reflexes in X-ray diffraction experiments, such as those that are typical of crystalline substances, but at best one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, particularly good builder properties may very well also be achieved when the silicate particles supply washed-out or even sharp diffraction maxima in electron diffraction experiments.
- X-ray amorphous silicates of this kind, which likewise exhibit retarded dissolution compared with conventional water glasses, are described in the German patent application DE-A-44 00 024, for example.
- compressed/compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are preferred, in particular the overdried silicates preferably also occurring as carriers in the granules according to the invention or being used as carriers in the method according to the invention.
- Suitable inorganic builders are carbonates, in particular sodium carbonate.
- phosphates As builders, provided that the use thereof should not be avoided for ecological reasons.
- Sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
- the content thereof is generally no more than 25 wt. %, preferably no more than 20 wt. %, in each case based on the finished agent.
- tripolyphosphates even in small amounts up to a maximum of 10 wt. %, based on the finished agent, in combination with other builders result in a synergistic improvement of the secondary washing performance.
- the washing or cleaning agent is preferably free of phosphates.
- the washing or cleaning agent may also contain at least one enzyme.
- This at least one enzyme is preferably one or more enzymes which can develop catalytic activity in a washing or cleaning agent, in particular a protease, amylase, lipase, cellulase, hemicellulase, mannanase, pectin-cleaving enzyme, tannase, xylanase, xanthanase, ß-glucosidase, carrageenanase, perhydrolase, oxidase, oxidoreductase and mixtures thereof.
- Preferred hydrolytic enzymes include in particular proteases, amylases, in particular ⁇ -amylases, cellulases, lipases, hemicellulases, in particular pectinases, mannanases, ß-glucanases, and mixtures thereof.
- proteases are particularly preferred, and proteases are more particularly preferred.
- these enzymes are of natural origin; starting from the natural molecules, improved variants for use in washing or cleaning agents are available which are correspondingly preferably used.
- the enzymes to be used can also be formulated together with accompanying substances, for example from fermentation, or with stabilizers.
- washing or cleaning agents can additionally contain one or more of the abovementioned substances, in particular those from the group comprising bleach activators, pH adjusters, perfumes, perfume carriers, fluorescing agents, dyes, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors and dye transfer inhibitors. Suitable agents are known in the prior art.
- washing or cleaning agent ingredients is by no means exhaustive, but merely reflects the most essential typical ingredients of agents of this kind.
- temperatures of up to 95° C. or less, 90° C. or less, 60° C. or less, 50° C. or less, 40° C. or less, 30° C. or less or 20° C. or less are used in different embodiments of the invention. These specified temperatures relate to the temperatures used in the washing or cleaning steps.
- the method according to the invention therefore also comprises the step of dosing one or more auxiliaries into the surfactant-containing liquid flow.
- auxiliaries can be dosed into the surfactant-containing liquid flow before or after the dye solution has been dosed.
- the auxiliary or auxiliaries are preferably dosed into the surfactant-containing liquid flow before the dye solution, such that the dye solution is dosed into the surfactant-containing liquid flow as late as possible in relation to the entire preparation method. This has the advantage that only the smallest possible part of the facility comes into contact with the dye. If a change of color is desired, only a small part of the facility has to be cleaned.
- auxiliaries it is certainly possible for some of the auxiliaries to be dosed before the dye solution, and for some of the auxiliaries, such as in particular enzymes or fragrances, to be dosed after the dye solution.
- washing or cleaning agents according to the invention which are obtained by means of the above-described method are a further aspect of the present invention. These washing or cleaning agents are thus free from preservatives, without this however impairing the visual properties or microbial impurities in any way.
- a further aspect of the present invention is providing a preservative-free dye solution.
- the dye is first predissolved in water in a low concentration, and the premixture obtained in this way is subsequently diluted in a non-aqueous organic solvent, the content of the organic solvent being at least 70 wt. % based on the total weight of the dye solution.
- the content of organic solvent is preferably 80 wt. %, in particular 90 wt. % or more.
- the organic solvent is a non-aqueous solvent.
- Preferred non-aqueous solvents include monovalent or polyvalent alcohols, alkanol amines or glycol ethers.
- the solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol-n-butylether, diethylene glycol hexyl ether, diethylene glycol-n-butylether acetate, ethylene glycol propyl ether, ethylene glycol-n-butylether, ethylene glycol hexyl ether, ethylene glycol-n-butylether acetate, triethylene glycol
- the obtained mixture was added to a masterbatch consisting of surfactants. After the remainder of the ingredients were subsequently added, a magenta-colored final product was obtained that complies with specifications.
- the obtained mixture was added to a masterbatch consisting of surfactants and further active substances and auxiliaries, inter alia, from the group of solvents, optical brighteners and complexing agents. After the remainder of the ingredients were subsequently added, a final product was obtained that complies with specifications.
- the dye mixture proved to be stable in a microbial load test. It was not necessary to add preservatives.
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Abstract
Description
-
- a) providing a preservative-free dye solution, the dye first being dissolved in water and this premixture subsequently being diluted in a non-aqueous organic solvent, the content of the organic solvent being at least 70 wt. % based on the total weight of the dye solution,
- b) dosing the dye solution obtained in this way into a surfactant-containing liquid flow.
in which R′ and R″, independently of one another, are H or alkyl, and together contain 6 to 19, preferably 7 to 15, and in particular 9 to 13, C atoms. A more particularly preferred representative is sodium dodecylbenzene sulfonate.
R1—O-(AO)n—SO3 −X+ (A-1)
Liquitint ® Violet 129 | 7.63% | ||
Liquitint ® Pink PV | 1.1% | ||
Water | 9.13% | ||
1,2-propanediol | 82.14% | ||
Liquitint ® Cyan 15 | 2.11% | ||
Sanolin Tartrazine X90 | 0.67% | ||
Water | 9.72% | ||
1,2-propanediol | 87.5% | ||
Claims (13)
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